Lubricating oil thickened to a grease consistency with a mixture of an organo hydantoin and a siliceous thickening agent



,- Patented'Apr. 11, 1961 LUBRICATING OIL THICKENED TO A GREASE CONSISTENCY WITH A MIXTURE OF AN OR- GANO HYDANTOIN AND A SILICEOUS THICK- ENING AGENT Paul R. McCarthy, Allison Park, and Joseph J. McGrath;

Monroeville, Pa., assignors to Gulf Researcher Development Company, Pittsburgh, Pa., a corporation of Delaware N Drawing. Filed June 15, 1959, Ser. No. 820,104

9 Claims. (Cl. 25249.7)

This invention relates to improved lubricating compositions and more particularly to lubricants suitable for high temperature lubrication. The trend in design of modern aircraft has accentuated the need for greases which will lubricate anti-friction bearings operating at high rotational speeds and high temperatures. While considerable progress has been made in recent years in producing improved aircraft greases some difi'iculty has been encountered in produc-' ing a grease which will effectively lubricate'bearings operating at high rotational speeds and high temperatures for prolonged periods of time. Conventional aircraft greases currently available have failedto meet the stringent'r'equirements on such a lubricant. r

We have discovered that a lubricating composition'having improved lubricating characteristics for an extended periodof time when used to lubricate bearings operatto; about 60 percent by weight of the total composition.

ing atan elevated temperature under high rotational speeds can be obtained by incorporating into a lubricating oil in 'oil thickening proportions a mixture of an organo hydantoin having the following structural formula:

wherein-R is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals, at least one R being a carbocyclic radical and a secondary organophilic siliceous oil thickening agent. Thus, the improved lubricating composition of our invention'compriscs a dispersion in a lubricating oil of a sufficient amount to thicken the lubricating oil to a grease consistency of a mixture of an organo hydantoin of the type designated by the above structural formula and an organophilic sili-' ceous oil thickening agent.

It will be noted that at least one of the Rs in the above formula must be a carbocyclic radical. So long as this requirement is satisfied, the remaining Rs may be alkyl, aryl, alkaryl, aralkyl or cycloalkyl radicals. It is preferred, however, that both of the Rs be carbocyclic "radicals, especially phenyl radicals, because of the increased resonance or thermal stability contributedto the compound byv such radicals. 4 Y,

The amount of the combined organo hydantoin and the organophilic siliceous material which we use is an amount suflicient to thicken the lubricating oil to a grease consistency. In general, this amount comprises about 10 The weight ratioof the hydantoin compound to the organophilic siliceous material will vary depending upon the characteristics desired in the ultimate composition.

In general, however, the ratio of hydantoin compound to the organophilic siliceous material is between about 1:1 and about 20: 1'.

The organo hydantoins which we prefer are those wherein the sum of the carbon atoms in the R groups is 7 to 18. Thus, typical hydantoins within our preferred class are S-methyl-S-phenyl hydantoin; S-ethyl-S- phenyl hydantoin; 5-propyl-5-phenyl hydantoin; 5-butyl- S-phenyl hydantoin; 5 -amyl-5-phenyl hydantoin; S-hexyl- S-phenyl hydantoin; S-cyclohexyl-S-phenyl hydantoin; 5- n-octyl-S-phenyl hydantoin; S-isooctyl-S-phenyl hydantoin; 5,-5.-,dip henyl hydantoin; S-methyl-S-cresyl hydantoin; S-noctyl-S-cresyl hydantoin; S-isooctyl-S-eresyl hydantoin; 5, 5-cl icresyl hydantoin; S-methyl-S-benzyl hydantoin; 5.11. octyl-S-benzyl hydantoin; S-isooctyl-S-benzyl hydantoin; 5,5-dibenzyl hydantoin; S-cresyl-S-phenyl hydantoin; 5- methyl-S-cyclopentyl hydantoin; 5,5-dicyclopentyl hydantoin; z5-methyl-5-cyclohexyl hydantoin; S -tertiary butyl- S-cyclohexyl hydantoin; S-isooctyl-S-cyclohexyl hydantoin; 5,5-dicyclohexyl hydantoin; S-methyl-S-naphthyl hydantoin; 5-isooctyl-5-naphthy1 hydantoin; and the like.

The amount of the organo hydantoin used may vary over wide limits depending upon the particular oil with which the hydantoin compound is to be blended and upon the properties desired in the final lubricating composition. ,While as much as 50 percent by weight of the total composition may comprise the hydantoin com-. pound, we prefer to use smaller amounts, that is,'in the order of about 10 to 40 percent by weight. It should be understood, however, that, depending upon the consistency of the composition desired and upon the organophilic siliceous material used in combination therewith, less than 10 percent or more than 50 percent of the hydantoin compound may be employed.

Theorganophilic siliceous materials which we employ in the lubricating composition of this invention are exemplified by bentonite-organic base compounds known commercially as. bentones and finely divided organo-siliceous solids such as the esterified siliceous solids known commercially as Estersils. The amount of the organophilic siliceous material employed may vary over Wide limits depending upon the particular compound employed, the particular'oilwith which the siliceous compound is blendedand, the properties desired in the ultimate composition. jWhile the organophilic siliceous material may comprise as much as 20 percent by weight of the total composition, we prefer to use smaller amounts, that, is,

in the order of about 1 to about 10 percent by weight. It should be understood, however, that depending upon the consistency of the composition desired and upon the organo hydantoin content of the composition less than 1 percent or more than 10 percent of the organo philic siliceous material can be employed. 17;;

Typical bentonite-organic base compounds employed in accordance with the invention are compoundsieorm posed of a montmorillonite mineral in which-at least 1 a part of the cationcontent of the mineral has been replaced by an organic base. Clays that swell at least to some extent on being contacted with water and contain as a primary constituent a mineral of the group known as montmorillonites are generally referred to as bentonites. Such clays, which contain exchangeable alkali metal atoms either naturally or after treatment, constitute the raw materials employed in making the bentonite-organic base compounds used in the compositions of this invention. So far as known, all naturally occurring montmorillonites contain some magnesium and certain of them, as exemplified by Hector clay, contain u hi ar nt e 9 m iu ha h ar e y have magnesium in place of the aluminum content characteristic of the more typical montmorillonites.

The bentonite-organic base compounds are preferably prepared as described in US. Patent No. 2,033,856, issued March 10, 1936, by bringing together the bentonite and the organic base in the presence of aqueous mineral acid to effect base exchange. The organic bases should preferably be titratable with mineral acids. Among these reactive bases are many alkaloids, and cyclic, aliphatic, and heterocyclic amines. The bentonite-organic base compounds used in preparing the lubricating compositions of this invention are preferably those prepared by bringing together a bentonite clay and such organic bases as aliphatic amines, their salts, and quaternary ammonium salts. Examples of such amines and salts are: decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, hexadecyl ammonium acetate, octadecyl ammonium acetate, dimethyldioctyl ammonium acetate, dimethyldidodecyl ammonium acetate, dimethyldodecylhexadecyl ammonium acetate, dimethyldicetyl ammonium acetate, dimethylhexadecyloctadecyl ammonium acetate, dimethyldioctadecyl ammonium acetate, and the corresponding chlorides and quaternary ammonium chlorides. The organic bases employed should be such as to impart substantial organophilic properties to the resulting compounds. The preferred bentonite compounds are prepared from quaternary ammonium compounds in which the N-substituents are aliphatic groups containing at least one alkyl group with a total of at least 10' to 12 carbon atoms. When aliphatic amines are used they preferably contain at least one alkyl group containing at least 10 to 12 carbon atoms.

While the long chain aliphatic amine bentonite compounds are readily dispersible in practically all oil bases, dispersion of the short or single chain aliphatic amine bentonite compounds, in the oil, particularly mineral oils and synthetic oils other than ester lubricants, can be facilitated by the use of one or more solvating agents. Suitable solvating agents are polar or: ganic compounds such as organic acids, esters, alcohols, ethers, ketones, and aldehydes, especially low molecular weight compounds of these classes. Examples of suitable solvating agents are: ethyl acetate, acetic acid, acetone, methyl alcohol, ethyl alcohol, benzoyl chloride, butyl stearate, coconut oil, cyclohexanone, ethylene dichloride, ethyl ether, furfural, isoamyl acetate, methyl ethyl ketone, and nitrobenzene. In cases where the use of a solvating agent is desirable for effecting more rapid and more complete dispersion of the organic bentonite compound in the oil, ordinarily only a relatively small amount of such agent may be necessary. However, as much as about 5 percent by weight based on the amount of the bentonite compound can be used.

Typical estersils employed in accordance with the invention are described in U.S. Patent No. 2,657,149, is-

sued October 27, 1953, to R. K. Iler. The estersils'are organophilic solids made by chemically reacting primary or secondary alcohols with certain siliceous solids. In brief, the estersils are powders or pulverulent materials the internal structure or substrate of which have an average specific surface area of from 1 to 900 square meters per gram. The substrate has a surface of silica which is coated with )R groups, the coating of -0R groups being chemically bound to the silica. R is a -----a. 79,4eo e e hydrocarbon radical of a primary or secondary alcohol containing from 2 to 18 carbon atoms. The carbon atom attached to the oxygen is also attached to hydrogen.

The estersil substrates are solid inorganic siliceous materials which contain substantially no chemically bound organic groups prior to esterification. The substrates are in a supercolloidal state of subdivision, indicating that whatever discrete particles are present are larger than colloidal size. In general, the supercolloidal substrates have at least one dimension of at least 150 millimicrons. The supercolloidal particles may be aggregates of ultimate units which are colloidal in size.

The estersils which we employ are advantageously those in which the ultimate units have an average diam: eter of 8 to millimicrons. The substratesadvantageously have specific surface areas of at least 'square meters per gram and preferably at least 200 square meters per gram.

The estersils made from most alcohols become organophilic-when they contain more than about ester groups per square millimicrons of surface of internal structure. They become more organophilic as the ester groups increase. Thus, the products which contain 100 ester groups per 100 square millimicrons of substrate surface are more organophilic than those that contain only 80 ester groups. When the estersils contain at least 200 ester groups per 100 square millimicrons of substrate surface, the estersils not only are. organophilic but also are hydrophobic. Thus, the more highly esterified products are particularly desirable where the lubricant made therefrom comes in contact with water. When 6 to C alcohols are usedin preparing the estersils, the estersils. may contain from 300 to 400 ester groups per 100 square millimicrons of substrate surface. Thus, a preferred group of estersils are those prepared from the C to G alcohols. The estersils, as noted above, are powders or pulverulent materials. The estersil powders are ex: ceedingly fine, light and fluffy. The bulk density of preferred estersils is in the order of 0.15 to 0.20 gram per cubic centimeter at 3 pounds per square inch and in the order of about 0.30 gram per cubic centimeter at 78 pounds per square inch. The estersils are available commercially and thus the estersils per se and their preparation constitute no part of this invention.

The lubricating oil in which the organo hydantoin and the secondary thickening agent are incorporated is pref erably a lubricant .of the type best suited for the particular use for which the ultimate composition is designed. Since many of the properties possessed by the lubricating oil are imparted to the ultimate lubricating composition, we advantageously employ an oil which is thermally stable at the contemplated lubricating temperature. Some mineral oils, especially hydrotreated mineral oils, are sufficiently stable to provide a lubricating base for preparing lubricants to be used under moderately elevated temperatures. Where temperatures in the order of 400 F. and above are to be encountered, synthetic oils form a preferred class of lubricating bases because of their high thermal stability. By the term synthetic oil we mean an oil of non-mineral origin. The synthetic oil can be an organic ester which has a majority of the properties of a hydrocarbon oil of lubricating grade such as di-Z-ethylhexyl sebacate, dioctyl phthalate and dioctyl azelate. Instead of an organic ester, we can use polymerized olefins, copolymers of alkylene glycols and alkylene oxides, polyorgano siloxanes and the like.

The liquid polyorgano siloxanes because of their exceedingly'high thermal stability form a preferred group of synthetic oils to which the organo hydantoin and organophilic siliceous materials are added. These polyorgano siloxanes are known commercially as silicones and are. made up of silicon and oxygen atoms wherein the silicon atoms may be substituted with alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals. Exemplary of such com pounds are the dimethyl silicone pelymers, diethyl ailicone polymers, ethyl-phenyl silicone polymers and methylphenyl silicone polymers.

If desired, a blend of oils of suitable viscosity may b employed as the lubricating oil base instead of a single oil by means of which any desired viscosity may be'secured. Therefore, depending upon the particular use for which the ultimate composition is designed, the lubri steady, state condition at the test temperature; (2 an increase in temperature at the test bearing of 20 F.

lubricating oil, the organo hydantoin and the secondary thickener together with a solvating agent and conventional lubricant additives, if desired, are mixed together at room temperature for a period of 10 to '30 'minutesto form a slurry. During this initial mixing period some thickening is evidenced. Some lumps may be formed. The slurry thus formed is then subjected to a conventional milling operation in a ball mill, a colloid mill, homogenizer or similar device used in compounding greases togive the desired degree of dispersion. In the illustrative compositions of this invention, the slurry was passed twice, by means of a pump, through a Premier colloid mill set at a stator-rotor clearance of 0.002 inch. Maximum thickening occurred on the second pass through the 1 The lubricating composition of this invention can contain conventional lubricant additives, if desired, to improve other specific properties of the lubricant without departing from the scope of the invention. lubricating composition can contain a filler, a corrosion and-rust inhibitor, an extreme pressure agent, an antioxidant, a metal deactivator, a dye, and the like.

Whether or not such additives are employed and the amounts thereof depend to a large extent upon the severity of the conditions to which the composition is subjected and upon the stability of the lubricating oil base in the first instance. Since the polyorgano siloxanes, for example, are in general more stable than mineral oils, they require the addition of very little, if any, oxidation inhibitor. When such conventional additives are used they are generally added'in amounts between about 0.01 and 5 percent by weight based on the weight of the .total composition.

-In order to illustrate the lubricating characteristics at an elevated temperature and high rotational speeds, grease compositions of the invention were subjected to the test procedure outlined by the Coordinating Research. Council Tentative Draft (July 1954), Research Tech-.

nique for the Determination of Performance Characteristics of Lubricating Grease in Antifriction Bearings at Elevated Temperatures, CRC Designation L35.' According to this procedure, 3 grams of the grease to be tested are placed in a bearing assembly containing an eight-ball SAE No. 204 ball bearing. The bearing assembly which is mounted on a horizontal spindle is subjected to a radial load of 5 pounds. The portion of the spindle upon which the test bearing assembly is located is encased in a thermostatically controlled oven. ,By this means the temperature of the bearing can be maintained at a desired elevated temperature which in the tests reported hereinafter was 400 F The spindle is driven by a constant belt-tension motor drive assembly, capable of giving spindle speeds up to 10,000 revolutions per minute. The spindle is operated on a cycling schedule consisting of a series of periods, each: period consisting o'f'20 hours running time and'4 hours shutdown time. The test continues until the lubricant fails. The lubricant is considered to have failed when any one of the following conditions occurs, (1) spindle input power increases to a valueapproximately 3.00 percent. abovethe over the test temperature during any portion of a cycle; or (3) the test bearing locks or the drive belt slips at the start or during the test cycle.

The oil used in preparing the lubricating compositions summarized in Table I was a synthetic oil known commercially as GE Silicone 81717. GE Silicone 81717 is marketed by General Electric Company and is a waterwhite to amber liquid polymer ofthe general formula It has a viscosity at 65" F. of 3487 centistokes, at 0 F. of 390 centistokes, at 100 F. of 71.3 centistokes, at 210 F. of 22 centistokes and at 700F. of 1.9 centistokes. The Estersil GT employed is marketed by E. I. du Pont W de Nemoursand Company and consists of an amorphous silica coated with approximately 340 butoxy groups per square millimicrons of surface. The product is a white granular solid comprising 88 to 89 percent SiO having an ultimate particle size of 8 to 10 millimicrons. The surface area comprises about 285 to 335 square meters per gram. The product has a pH in a 50-50 methanolwater mixture of 8.0 to 9.0 and a bulk density of 19 to 20 pounds per cubic foot.

In preparing the lubricating compositions, the oil, the 5,5-diphenyl hydantoin and the dimethyldicetylammonium bentonite or estersil were mixed at room temperature for a period of 10 to 30 minutes. The slurry thus formed was passed twice through a Premier colloid mill set at a statorrotor clearance of 0.002 inch. The thickened lubricating compositions thus prepared had the following approximate make-up.

CompositiomPercent By, Weight The long performance life of the compositions of the invention at a high rotational speed and a high temperature is self evident from the above data. When Composi-' tion A was subjected even to a more serere test using Pope spindles and an MRC 204 S-17 bearing at 400 F. and

20,000 revolutions per minute no failure was recorded even after 502 hours of operation. I

An additional .lubricating composition of the invention similar to Composition A was prepared except 30 parts of the GE Silicone 81717 were replaced with 30 parts of DC 550 Fluid marketed by Dow-Corning Corporation.

This fluid is a methylphenyl-siloxane polymer having as'.

typical characteristics a viscosity at 100 F. of .300 to 400 SUS, a viscosityetemperature coefficient of 0.75, a freezing: point of 54 F., a flash point of 600 F. and a specific 1 gravity 25 C./25C. of 1.08. When this composition was tested in the more severe test referred to above at 20,000 revolutions per minute, there was no failure even after 548 hours of operation.

Other lubricating compositions within the scope of the invention are illustrated in Table II.

Table II' Composition, Percent O D E F G H I J K 'L M N O P Q By Weight Lubricating;

Do 550 Fluid 64 7o 70 64 64 47.5 70 so Dr-2-ethylhexylsebacate... 7o 70 so eo 7o 64 e Organo flydantoin:

M ethy-5-pheny1 hydan- 5 Is o oct 1 fi e clohe 1 24 20 h danib y 24 25 5,5-Dicyclohexyl hydantoin 32 35 ipheuylhydantoine- 32 30 5o so 32 36 Secondary Thickener:

Dimethyldicetylammonium bentorii e 4 10 10 10 6 4 Dimethyldidodecylammoniumbentonife 6 5 Dimethyldioctylammonlum bentonite 6 1O Dimethyldioctadecylammouium bentonite 6 5 Estersil GT. 4' 2.5 4 Ratio of hydautoin to seconddary'thickener 8:1 4:1 4:1 5:1 8:1 20:1 2:1 1:1 2:1 5:1 7:1 3:1 5:1 8:1 9:1

While our invention has been described with reference wherein R is selected from the group consisting of alkyl, fo'various specific examples and embodiments, it will be aryl, alkaryl, aralkyl and cycloalkyl radicals, at least one understood that the invention is not limited to such ex- 25 R being a carbocyclic radical and the sum of the carbon amples and embodiments and may be variously practiced atoms in the R groups is 7 to 18 and an organophilic within the scope of the claims hereinafter made. bentonite-organic base compound, the weight ratio of the We claim: organo hydantoin to the organophilic bentonite-organie 1. A- lubricating composition comprising a dispersion base compound in said mixture being about 1:1 to 20:1. in a lubricating oil of a suflicent amount to thicken the 7. The lubricating composition of claim 6 wherein the lubricating oil to a grease consistency of a mixture of an organo hydantoin is 5,5-diphenyl hydantoin and the hen-- organohydantoin having the following structural formula: tonite-organic base compound is dimethyldicetylammoni R H umbentonite.

7 I 8. A lubricating composition comprising a dispersion in a liquid polyorgano siloxane of a sufficient amount to C0 thicken the polyorgano siloxane to a grease consistency 00N of a mixture of an organo hydantoin having the followi ing structural formula: where R is selected from the group consisting of alkyl, 40. aryl, alkaryl, aralkyl and cycloalkyl radicals, at least one R CN R being a carbocyclic radical and the sum of the carbon 00 atoms in the R groups is 7 to 18 and an organophilic o siliceous oil thickening: agent, the weight ratio of the organo hydantoin to the organophilic siliceous material H sald i about f} to 20:13 wherein R is selected from the group consistingv of alkyl, 11115 lubncatmg compcfsltlon clalm f" the aryl, alkaryl, aralkyl and cycloalkyl radicals, at least one comblfled hydantom' and organophlhc slllceous R being a carbocyclic radical and the sum of, the carbon material compnses about 10 to 60 percent by weight of awms the R groups is 7 to 18 and an organbphilic the total f l estersil, thewe'ight ratio of the organo hydantoin-tothe 1 lulinfiatmg oomposl? of 01mm 1 wheremthe organophilic estersil in said mixture being about 1:1 to lubncatmg 1 P 20: 1 said organophilic estersil comprising asupercolloidal F F Q of Clam Wherem substrate coated with OR' groups, the substratehaving: a organophilic siliceous 011 thickening agent is a bentomtesurface, of Silica and having a Specific surface area: f organ; base i f from 25' to 900 square meters per gram, the coating of 5:. The lubricating composition of claim 1 wherein the groups being chemically bound to Said ili and organophilic siliceous oil, thickening agent is an organobeing a hydrocarbon radical of f o 3 to 5 carbon phlfic esters comprising a supercouqldal Substrate f i atoms, wherein the carbon atom attached: to oxygen is with -,OR groups, the substrate having a surface of silica also attached to hydrogem and having a specific'surface.awa of from f 9. The lubricating composition of claim 8 wherein the meter? Per gram ft P gmuPS bemg organo hydantoin is 5,5-diphenyl hydantoin and the orchemical-ly bound to said srlrcaandR being a hydrocarganophflic estersil is an amorphous silica coated i bon radical of from 2v to 18 carbon atoms, wherein the about 340 butoxy groups per 100 Square millimicmns of carbon attached to oxygen is also attached to hydrogen. Surface 6. A lubricating composition comprising adispersion in a liquid polyorgano siloxane of a suflicient amount to References, Cited in h file f hi atent thicken the polyorgano siloxane to a grease consistency'of p g p 7 a mixture of an organohydantoinqhaving the following UNITED STATES PATENTS structural formula: 2,320,763 Hughes et a1 Jan. 21,1958

R 11 2,875,152 Van Scoy gm-12g, ec. 1 2,917,457 Prerss oo OTHER REFERENCES OG'-N- Chem. Abstracts, vol. 41, page 7392b, 1947.

g; Chem: Abstracts, vol, 47, page 5894d, 1953.v

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 979,460 I A ril 11, 1961 I Paul R. McCarthy et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patentv should read as corrected below.

Column 2 line 45, for Ubentones" read Bentones Signed and sealed this 5th day of December 1961.v

' (SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer V Commissioner of Patents USCOMM-DC- 

1. A LUBRICATING COMPOSITION COMPRISING A DISPERSION IN A LUBRICATING OIL OF A SUFFICENT AMOUNT TO THICKEN THE LUBRICATING OIL TO A GREASE CONSISTENCY OF A MIXTURE OF AN ORGANO HYDANTOIN HAVING THE FOLLOWING STRUCTURAL FORMULA: 